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Derivatives  of  Anthraquinone*     J-Alkyl- 

Thio-Ether-S-Sulfpnic  Acids  and 

^5-Dialkyl-Dithio-Ethers 


JUI24 


A  DISSERTATION 

SUBMITTED  TO  THE  BOARD  OF  UNIVERSITY  STUDIES  OF  THE 

JOHNS  HOPKINS  UNIVERSITY  IN  CONFORMITY  WITH 

THE  REQUIREMENTS  FOR  THE  DEGREE  OF 

DOCTOR  OF  PHILOSOPHY 


BY 


COLIN   MACKENZIE  MACKALL 
June,  1920 


EASTON,  PA.: 
ESCHBNBACH  PRINTING  Co. 

1922 


Derivatives  of  Anthraquinone*     J-Alkyl- 

Thio-Ether-5-Sulfonic  Acids  and 

J-5-Dialkyl-Dithio-Ethers 


A  DISSERTATION 


SUBMITTED  TO  THE  BOARD  OF  UNIVERSITY  STUDIES  OF  THE 

JOHNS  HOPKINS  UNIVERSITY  IN  CONFORMITY  WITH 

THE  REQUIREMENTS  FOR  THE  DEGREE  OF 

DOCTOR  OF  PHILOSOPHY 


BY 


COLIN  MACKENZIE  MACKALL 
June,  1920 


EASTON,  PA.: 
ESCHENBACH  PRINTING  Co. 

1922 


TABLE  OP  CONTENTS 

Acknowledgment 4 

Introduction 5 

Historical 5 

Outline  of  Present  Investigation 6 

Materials 6 

Analytical 7 

The  Compounds  Obtained 7 

I.     Anthraquinone-l-alkyl-thio-ether-5-sulfonic  acids 8 

II.     Anthraquinone-l-5-dialkyl-dithio-ethers 10 

III.     Anthraquinone-l-5-dialkyl-disulfones 12 

Biography 13 


ACKNOWLEDGMENT 

The  author  wishes  to  record  his  sense  of  grateful  appreciation  of  the 
encouragement,  kindly  advice  and  helpful  criticism  of  Professor  E.  Emmet 
Reid  under  whose  direction  this  investigation  was  conducted. 

He  also  wishes  to  express  his  thanks  for  instruction  received  from 
Doctors  Remsen,  Frazer,  Lovelace,  Patrick,  Lloyd  and  Swartz  during  his 
course  at  this  University. 

He  desires  to  thank  Doctors  Thornton  and  Milligan  for  advice  and 
assistance. 


DERIVATIVES    OF  ANTHRAQUINONE.     1-ALKYL-THIO-ETHER- 
5-SULFONIC   ACIDS  AND    1-5-DIALKYL-DITHIO -ETHERS.1 

Introduction. 

The  original  object  in  taking  up  the  study  of  anthraquinone  sulfonic 
acids  was  to  obtain  derivatives  which  could  be  used  for  their  ready  separa- 
tion and  identification.  This  object  was  only  partially  attained  but  the 
reaction  tried  proved  interesting  and  the  products  obtained  appeared 
worthy  of  study,  so  the  investigation  was  shifted  from  its  original  purpose 
and  extended  in  other  directions. 

On  account  of  the  instability  of  the  esters  of  sulfonic  acids  the  methods 
used  for  the  identification  of  carboxy  acids2  were  not  promising  and  our 
efforts  were  directed  to  the  replacement  of  the  sulfonic  groups. 

It  was  known  that  the  sulfonic  acid  group  of  a-anthraquinone  sulfonic 
acids  can  be  replaced  by  methoxy3  or  phenoxy4  groups,  and  that  the  result- 
ing compounds  Ci4H7O2.OCH3  and  Ci4H7O2.OC6H5  are  crystalline  and  have 
definite,  though  rather  high  melting  points.  Hence  it  was  thought  that 
a  compound  of  the  type  Ci4H7O2.SR  would  be  of  service.  AT-butyl  mercap- 
tan  was  used  as  being  readily  available,  and  it  was  thought  probable  that 
the  compound  Ci4H7O2.SC4H9  would  have  a  low  melting  point,  since 
sulfur  compounds  usually  melt  lower  than  the  corresponding  oxygen 
compounds,  and  since  butyl  derivatives  are  apt  to  melt  considerably  lower 
than  methyl,  and  much  lower  than  phenyl.  The  desired  reaction  was  found 
to  take  place  readily,  although  not  quantitatively,  when  the  sulfonic 
acid  group  is  in  the  a-position.  The  resulting  compounds  were  found 
to  have  convenient  melting  points  suitable  for  the  identification  of  anthra- 
quinone- a-sulfonic  acid,  and  anthraquinone- 1,5-  and  -1,8-disulfonic  acids. 

Our  study  has  been  extended  to  the  derivatives  of  other  mercaptans. 

Historical. 

Anthraquinone  aliphatic  thio-ether  sulfonic  acids  and  dithio-ethers 
may  be  prepared  by  the  action  of  aliphatic  mercaptans  on  anthraquinone 
sulfonic  acids  in  alkaline  solution.6  In  this  way  Bayer  and  Company  pre- 

1  Revised  September  1922. 

2  /.  Am.  Chem.  Soc.,  39,  124,  304,  701,  1727    (1917);   41,    75    (1919);  42,   1043 
(1920);  and  43,  629  (1921). 

8  Bayer  and  Co.,  Ger.  pat.  156,762. 
4  Bayer  and  Co.,  Ger.  pat.  158,531. 
s  Bayer  and  Co.,  Ger.  pat.  224,589. 


6 

pared    anthraquinone-l-ethyl-thio-ether-5-sodium   sulfonate    and    1,5-di- 
ethyl-thio-ether. 

Gattermann6  has  shown  that  the  nitro  group  is  replaceable  by  the 
alkoxy  group  when  treated  with  sodium  alcoholate,  thus, 

A.NO2  +  NaOC2H6  — >•  A.OC2H6  +  NaNO2 

representing  the  anthraquinone  residue  by  A.  He  attempted  to  carry 
out  the  analogous  reaction  with  aliphatic  mercaptans  in  order  to  obtain 
anthraquinone  thio-ethers,  but  was  hindered  by  the  reduction  of  the  nitro 
group  to  the  amino  group.  On  the  other  hand,  he  found  that  treatment 
with  alkali  aromatic  mercaptides  readily  caused  a  quantitative  replace- 
ment of  the  nitro  group  with  the  formation  of  aromatic  thio-ethers. 
A.NO2  +  NaSC6H6  — *•  A.SC6H6  +  NaNO3 

Gattermann7  has  also  prepared  anthraquinone  aliphatic  thio-ethers 
and  thio-ether  sulfonic  acids  indirectly  by  diazotizing  amino-anthra- 
quinones,  or  amino-anthraquinone  sulfonic  acids  in  cone,  sulfuric  acid. 
Subsequent  treatment  of  the  diazo  compound  with  potassium  thiocyanate 
yielded  anthraquinone  thiocyanate  which  on  boiling  with  alcoholic  potash 
gave  the  mercaptan,  which  with  alkyl  halide  yielded  the  thio-ether  or 
thio-ether  sulfonic  acid.  In  this  way  he  prepared  anthraquinone- a:  - 
methyl-thio-ether ;  anthraquinone-  a-ethyl-thio-ether ;  anthraquinone- 1  - 
methyl- thio-ether-5-potassium  sulfonate;  and  anthraquinone-1-methyl- 
thio-ether-8-potassium  sulfonate,  thus, 

A.NO2  — >  A.NH2  — >  A.N2C1  — >  A.SCN  — >  A.SH 
A.SNa  +  BrCH,  — >  A.SCH,  +  KBr 

Outline  of  Present  Investigation. 

We  have  found  that  anthraquinone-l-5-disulfonic  acid,  on  heating  with 
alkyl  mercaptans  in  alkaline  solution,  reacts  readily  to  form  anthraqui- 
none-1-5-thio-ether-sulfonic  acids  and  1-5-dialkyl-dithio-ethers,  the  sul- 
fonic groups  being  replaced  in  turn. 

Materials 

The  anthraquinone- 1-5-disodium  sulfonate  was  obtained  through  the 
courtesy  of  E.  I.  du  Pont  de  Nemours  and  Company.  The  methyl  mer- 
captan was  generated  as  required  by  dropping  dimethyl  sulfate  into  warm 
sodium  hydrosulfide,  which  was  prepared  by  warming  crystallized  sodium 
sulfide,  Na2S.9H2O,  to  about  90°  and  saturating  with  hydrogen  sulfide. 
The  ethyl  mercaptan  was  prepared  in  a  similar  manner  using  sodium  ethyl 
sulfate.  The  propyl,  butyl  and  iso-amyl  mercaptans  were  prepared  by  the 
catalytic  method  of  Kramer  and  Reid.8 

6  Bayer  and  Co.,  Ger.  pat.  75,054. 

7  Ann.,  393,  113  (1912). 

8  Kramer  and  Reid,  J.  Am.  Chem.  Soc.,  43,  880  (1921). 


Analytical. 

1.  Water  of  Hydration. — One-g.  samples  were  exposed  to  an  atmos- 
phere of  50%  humidity9  for  48  hours,  then  heated  to  constant  weight  in  a 
vacuum  at  110°,  2  to  4  hours  being  generally  sufficient  to  remove  all  the 
water.     Analyses  for  sulfur  and  metals  were  made  on  the  dry  samples. 

2.  Sulfur. — Sulfur    was  determined  by  means  of    the  Parr  bomb,10 
using  a  0.2  g.  sample  and  5  g.  of  sodium  peroxide,  with  subsequent  pre- 
cipitation of  barium  sulfate. 

3.  Sodium,  Barium,  Strontium,  Calcium. — One-half  g.  samples  were 
ignited  in  a  platinum  crucible  until  the  carbon  was  burned  off  as  com- 
pletely as  possible.     The  residue  was  then  evaporated  with  cone,  sulfuric 
acid,    and    re-ignited  with   ammonium  carbonate  to   constant  weight. 
The  metal  was  weighed  as  the  sulfate. 

The  Compounds  Obtained. 

The  anthraquinone-thio-ether  sodium  sulfonates  are  moderately  soluble 
in  water,  the  derivatives  of  the  lower  mercaptans  being  more  soluble  than 
those  of  the  higher  mercaptans.  They  crystallize  from  water  in  orange 
or  orange-red  needles  containing  one  molecule  of  water  of  hydration. 
Salts  of  other  bases  are  highly  colored,  ranging  from  yellow  through 
through  shades  of  orange  to  red  and  are  mostly  well  crystallized. 

The  anthraquinone  dithio-ethers  are  insoluble  in  water,  slightly  soluble 
in  alcohol  and  soluble  in  benzene,  the  solubility  in  benzene  increasing 
with  the  size  of  the  alkyl  group.  When  crystallized  from  benzene  they 
form  lustrous  crystals  varying  in  color  from  light  yellow  to  red. 

The  corresponding  sulfones  are  high  melting,  slightly  yellow  crystalline 
powders. 

9  A  dead  air  humidor  containing  44%  H2SO4  was  used  to  obtain  this  humidity. 

10  Parr,  J.  Ind.  Eng.  Ghent.,  11,  230  (1919). 


I.    Anthraquinone-l-alkyl-thio-ether-5-sulfonic  Acid. 
O     SR 


NaO3S     O 

1.  Methyl  or  ethyl  mercaptans  were  passed  through  a  wide  tube  at  the  rate  of 
one  bubble  per  second  into  an  alkaline  suspension  of  anthraquinone-l-5-disodium  sul- 
fonate.     The  mixture  was  gently  boiled  and  vigorously  stirred  until  the  separation  of 
yellow  or  orange  crystals  of  anthraquinone-thio-ether-sodium  sulfonate  indicated  that 
the  reaction  was  complete.     The  reaction  must  be  interrupted  at  the  proper  moment 
to  prevent  the  formation  of  large  amounts  of  the  dithio-ether  by  the  replacement  of 
the  second  sulfonic  acid  group  by  the  thio-alkyl  group.     The  product  was  cooled,  fil- 
tered, washed  with  a  little  water,  dried  and  extracted  with  benzene  to  remove  the 
dithio-ether  which  was  always  formed  in  small  amounts.     The  crude  anthraquinone- 
thio-ether-sodium  sulfonates  were  recrystallized  from  water. 

2.  Anthraquinone-propyl-,   butyl-,   and   iso-amyl-thio-ether-sulfonic  acids  were 
prepared  by  refluxing  an  alkaline  suspension  of  anthraquinone-l-5-disodium  sulfonate 
with  slightly  more  than  the  calculated  amount  of  mercaptan.  The  products  were  puri- 
fied as  under  I,  1  above. 


PREPARATION   OP  ANTHRAQUINONE-I-ALKYL-THIO-ETHER-S-SODIUM  SULFONATES. 
l,5-RS.Ci4H602.SO3Na.H2O. 


Sulfonate. 

Water. 

NaOH. 

Alkyl. 

G. 

Cc. 

G. 

RSH. 

Methyl 

50 

400 

13 

gas 

Ethyl 

100 

600 

26 

gas 

Propyl 

50 

1000 

10 

12 

Butyl 

50 

500 

16 

15 

iso-Amyl 

100 

1000 

32 

34 

Time. 
Hrs. 

Yield. 
G. 

%. 

2 

30 

65 

1 

38 

42 

1 

23 

50 

7 

30 

62 

15 

55 

55 

ANALYSES  AND  PROPERTIES  OF  SODIUM  SALTS.     l,5-RS.Ci4H6O2.SO3Na.H2O. 


Water. 
Calc.       Found. 


Sodium. 
Calc.        Found. 


Alkyl. 

%• 

%. 

%• 

%. 

Methyl 

4.81 

4.86 

6.46 

6.27 

Ethyl 

4.64 

4.93 

6.21 

6.04 

Propyl 

4.48 

4.42 

5.98 

5.92 

Butyl 

4.33 

4.41 

5.77 

5.77 

iso-Amyl 

4.19 

4.26 

5.58 

5.43 

Color  and  form. 

orange-red  needles 
dark  orange-red  needles 
rich  orange-red  needles 
orange-red  needles 
orange-red  needles 


Barium,  Calcium  and  Strontium  Salts. — These  were  made  by  dissolving  the  sodium 
salts  in  hot  water  and  adding  the  calculated  amounts  of  the  chlorides  of  the  other  metals. 
The  resulting  salts  are  extremely  insoluble  and  are  purified  by  boiling  out  with  water. 


BARIUM  SALTS.     l,5-(RS.Ci4H6O2SO3)2Ba. 


Alkyl. 

Methyl 

Ethyl 

Propyl 

Butyl 

iso-Amyl 


Calc. 

%. 

17.09 
16.51 
15.97 
15.47 
14.99 


Barium. 


Found. 
%. 

17.00 
16.50 
15.58 
15.43 
14.56 


Color  and  form. 

red  needles 

red   crystal   powder 

orange-red  needles 

red  crystals 

red  crystals 


The  strontium  and  calcium  salts  also  were  made  of  the  butyl  acid,  the  strontium 
salt  being  anhydrous,  (Sr,  calc.  10.45;  found,  10.40).  The  calcium  salt,  unlike  the 
others  contains  4  molecules  of  water  of  crystallization,  showing  by  analysis  8.12% 
of  water  and  5.09%  of  calcium  compared  to  8.35  and  5.07%  respectively,  by  formula. 
The  barium  salt  is  a  deep  red  and  the  calcium  salt  an  orange-red,  while  the  strontium  salt 
is  intermediate. 

Aniline,  o-  and  p-Toluidine  Salts.  —  These  salts  were  made  by  adding  the  corre- 
sponding hydrochlorides  to  the  hot,  saturated  solutions  of  the  sodium  salts.  All  of  them 
are  very  insoluble  and  precipitate.  They  were  purified  'by  extraction  with  hot  water. 
They  all  separate  as  fine  yellow  needles  which  melt  with  decomposition  at  from  250°  to 
300°.  These  temperatures  are  not  sharp  enough  for  characterization  as  had  been  hoped. 
The  0-toluidine  salts  decompose  at  lower  temperatures  than  the  aniline  or  p-toluidine. 


ANIUNE,    0-Toi,uiDiNE    AND 


Alkyl. 
Methyl 


Ethyl 


Propyl 


Butyl 


iso-Amyl 


Base. 


SALTS. 


Decomp.  temp.          Calc. 


Sulfur. 


Aniline 

290-299 

o-Toluidine 

285-290 

£-Toluidine 

298-304 

Aniline 

276-285 

0-Toluidine 

264-274 

£-Toluidine 

276-285 

Aniline 

270-277 

o-Toluidine 

255-257 

^-Toluidine 

268-275 

Aniline 

257-259 

o-Toluidine 

234-237 

£-Toluidine 

256-260 

Aniline 

263-265 

0-Toluidine 

250-254 

p-Toluidine 

267-277 

15.00 
14.53 
14.53 
14.53 
14.08 
14.08 
14.08 
13.66 
13.66 
13.66 
13.26 
13.26 
13.26 
12.89 
12.89 


Pound. 

%. 

14.70 
14.75 
14.50 
14.30 
14.10 
14.25 
14.15 
13.75 
13.85 
13.80 
13.35 
13.10 
13.10 
12.80 
12.90 


10 


II.     1,5-Anthraquinone    Dialkyl    Dithio-ethers, 
O     SR  O      SR 


and 


RS    O 


R'S    O 


When  the  two  alkyl  groups  are  the  same,  these  may  be  obtained  directly  by  heatinj 
the  sodium  1,5-disulfonate  with  excess  of  alkali  and  mercaptan  for  a  long  time.  The> 
are  always  formed  to  a  greater  or  less  extent  in  the  preparation  of  the  intermediate 
thio-ether  sulfonates  described  above  and  are  obtained  by  extraction  of  the  crude 
products  with  benzene.  The  diethyl  and  dibutyl  compounds  were  obtained  in  this  way 
The  intermediate  monosulfonate  may  be  isolated  and  purified  and  the  second  alky 
group,  which  may  be  the  same  as  the  first  or  different,  introduced.  Of  course  the  mixec 
thio-ethers  must  be  prepared  in  this  way. 

The  alkyl  thio-ether  sodium  sulfonate  is  suspended  in  water,  containing  an  exces; 
of  caustic  soda  with  the  mercaptan,  and  the  mixture  boiled.  The  reaction  is  slow  or 
account  of  the  low  solubility  of  the  sodium  salts,  particularly  of  those  containing  th< 
higher  alkyl  groups.  It  is  best  to  introduce  the  lower  alkyl  group  first.  The  resulting 
di thio-ethers  are  extracted  with  hot  benzene  and  recrystallized  from  benzene,  or  alcohol 
or  mixtures  of  the  two.  The  details  of  the  various  preparations  are  given  in  tabulai 
form. 


PREPARATION  OF   I.S-ANTHRAQUINONB  DIALKYI,  DITHIO-BTHBRS. 

First 
alkyl. 

Methyl 


Ethyl 


Propyl 
tso-Amyl 


Alkyl 
introduced. 

Wt.             Vol. 
sulfonate.   water. 
G.              Cc. 

Caustic  Wt. 
soda.  RSH. 
G.         G. 

Time. 
Hours. 

Yield. 
G. 

Methyl 

5 

500 

2 

gas 

4 

4 

Ethyl 

10 

500 

4 

gas 

4 

1 

Propyl 

8 

500 

2 

6 

23 

5 

Butyl 

8 

500 

2 

4.6 

22 

5 

iso-Amyl 

8 

500 

2 

4.4 

6 

6 

Propyl 

5 

350 

2 

5 

30 

4 

Butyl 

5 

350 

2 

5 

30 

4 

iso-Amyl 

5 

300 

2 

5 

12 

4.5 

Propyl 

10 

750 

2 

6 

20 

7 

Butyl 

8 

750 

2 

6 

7 

3 

Butyl 

10 

1000 

2 

5 

41 

6.5 

iso-Amyl 

10 

300 

2 

5 

11 

2.5 

11 


PROPERTIES  AND  ANALYSES  OP  1,5-ANTHRAQuiNONE  DIALKYI,  DITHIO-BTHERS. 
Ci4H6O2(SR)2  AND  l,5-RS.CuH6O2.SR'. 


Alkyls. 


Sulfur. 


Methyl 


Ethyl 


Propyl 

Butyl 

iso-Amyl 


M.  p. 

OU11I 

Calc. 

-ii  . 

Found. 

•d 

%• 

%. 

Methyl 

Chars. 

21.35 

21.03 

Ethyl 

229 

20.40 

20.35 

Propyl 

209 

19.53 

19.45 

Butyl 

173.5 

18.73 

18.50 

iso-Amyl 

175 

17.99 

17.90 

Ethyl 

226.5 

19.53 

19.40 

Propyl 

188.5 

18.73 

18.65 

Butyl 

156 

17.99 

17.75 

iso-Amyl 

152 

17.31 

17.25 

Propyl 

227 

17.99 

18.30 

Butyl 

175 

17.31 

16.95 

Butyl 

159.5 

16.68 

16.65 

iso-Amyl 

134 

16.09 

15.80 

iso-Amyl 

158.5 

15.55 

15.59 

Color  and  form. 

red  needles 
yellow  needles 
orange  needles 
yellow  needles 
orange-yel.  leaflets 
orange  grains 
orange  grains 
red  crystals 
gold-yellow  plates 
orange  cryst.  powder 
orange  prisms 
yellow  needles 
orange  needles 
yellow  needles 


Comparing  these,  we  see  that  the  dimethyl  compound  has  the  highest  melting 
point  and  that  the  melting  point  is  progressively  lowered  as  heavier  alkyl  groups  are 
substituted  for  one  of  the  methyls.  Gattermann  gives  the  diethyl  thio-ether  as  melting 
at  230°. 


12 


III.     1 ,5-Anthraquinone  Dialkyl  Disulf  ones. 

O     SO2R  SO2R 

and 

O  R'OaS 

These  were  prepared  by  oxidizing  the  dithio-ethers  with  fuming  nitric  acid.  They 
separate  as  faintly  yellow  crystalline  powders,  when  their  nitric  acid  solutions  are 
poured  into  hot  water.  They  are  very  slightly  soluble  in  most  solvents. 


PROPERTIES  AND  ANALYSES  OP  I^-ANTHRAQUINONE  DIALKYL  DISULFONES,  l,5-CuH6Oj- 
(SO2R)2  AND  l,5-R'SO2.Ci4H6O2.SO2R. 


Alkyls. 


M.p. 


Sulfur. 
Calc.         Found. 


Form. 


Methyl 

Methyl 

chars. 

17.60 

17.53 

powder 

Ethyl 

>300 

16.95 

16.90 

fine  needles 

Propyl 

291 

16.34 

16.50 

crystalline  grains 

Butyl 

264 

15.78 

15.75 

crystalline  grains 

iso-Amyl 

266 

15.25 

15.00 

crystalline  grains 

Ethyl 

Ethyl 

269.5 

16.34 

16.40 

fine  needles 

Propyl 

243.5 

15.78 

15.65 

fine  needles 

Butyl 

194 

15.25 

15.45 

powder 

iso-Amyl 

198 

14.76 

14.80 

powder 

Propyl 

Propyl 

265 

15.25 

15.15 

fine  needles 

Butyl 

220 

14.76 

14.95 

crystalline  grains 

Butyl 

Butyl 

184.5 

14.30 

14.10 

crystalline  powder 

iso-Amyl 

203.5 

13.87 

14.00 

crystalline  powder 

iso-Amyl 

iso-Amyl 

202 

13.46 

13.50 

powder 

BIOGRAPHY 

Colin  Mackenzie  Mackall  was  born  at  Baltimore,  Maryland  on  Decem- 
ber 26,  1884.  He  received  his  primary  education  in  the  public  schools 
of  that  city,  and  graduated  from  the  Baltimore  City  College  in  1904.  He 
then  entered  the  University  of  Virginia,  from  which  Institution  he  received 
the  degrees  of  Bachelor  of  Arts  in  1909  and  Bachelor  of  Science  in  Chem- 
istry in  1910.  The  following  year  he  was  Assistant  Chemist  in  the  Bureau 
of  Chemistry,  U.  S.  Department  of  Agriculture,  and  in  attendance  upon 
courses  at  George  Washington  University.  Upon  the  completion  of  a 
thesis  in  absentia,  this  University  conferred  the  degree  of  Master  of 
Science  upon  him  in  1913. 

From  1911  to  1916  he  was  Professor  of  Chemistry  in  the  University  of 
the  South,  Sewanee,  Tennessee.  Resignining  his  position  in  order  to 
continue  his  studies,  he  entered  the  Johns  Hopkins  University  in  the 
Fall  of  1916  taking  Chemistry,  Physical  Chemistry  and  Mineralogy. 

He  entered  the  Officers'  Training  Camp  in  the  Summer  of  1917,  and  was 
commissioned  Captain,  Coast  Artillery  Corps,  and  went  overseas.  He 
was  transferred  to  the  Chemical  Warfare  Service,  and  served  as  Gas 
Officer  of  the  Second  Division,  Assistant  Gas  Officer  of  the  First  Corps, 
and  Assistant  Chief,  and  later  Chief,  of  Chemical  Warfare  Service,  Second 
Army.  He  was  promoted  to  Major  C.  W.  S.  in  September  1918. 

After  the  armistice  he  attended  the  University  of  Paris  for  one  semester, 
and  re-entered  the  Johns  Hopkins  University  as  a  University  Fellow  in 
the  Fall  of  1919. 


Mackall,C*I« 

Derivatives 
an thr equine  ne 


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